Layered cathode for molten carbonate fuel cell

ABSTRACT

A layered cathode structure for a molten carbonate fuel cell is provided, along with methods of forming a layered cathode and operating a fuel cell including a layered cathode. The layered cathode can include at least a first cathode layer and a second cathode layer. The first cathode layer can correspond to a layer that is adjacent to the molten carbonate electrolyte during operation, while the second cathode layer can correspond to a layer that is adjacent to the cathode collector of the fuel cell. The first cathode layer can be formed by sintering a layer that includes a conventional precursor material for forming a cathode, such as nickel particles. The second cathode layer can be formed by sintering a layer that includes a mixture of particles of a conventional precursor material and 1.0 vol % to 30 vol % of particles of a lithium pore-forming compound. The resulting layered cathode structure can have an increased pore size adjacent to the cathode collector to facilitate diffusion of CO 2  into the electrolyte interface, while also having a smaller pore size adjacent to the electrolyte to allow for improved electrical contact and/or reduced polarization at the interface between the electrolyte and the cathode.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Patent Application No. 62/773,477, filed Nov. 30, 2018 and entitled “Layered Cathode for Molten Carbonate Fuel Cell.” The entirety of the aforementioned application is incorporated by reference herein.

FIELD

A layered cathode structure suitable for use in a molten carbonate fuel cell is provided, along with methods for operating such a molten carbonate fuel cell.

BACKGROUND

This application discloses and claims subject matter made as a result of activities within the scope of a joint research agreement between ExxonMobil Research and Engineering Company and FuelCell Energy, Inc. that was in effect on or before the effective filing date of the present application.

Molten carbonate fuel cells utilize hydrogen and/or other fuels to generate electricity. The hydrogen may be provided by reforming methane or other reformable fuels in a steam reformer, such as a steam reformer located upstream of the fuel cell or integrated within the fuel cell. Fuel can also be reformed in the anode cell in a molten carbonate fuel cell, which can be operated to create conditions that are suitable for reforming fuels in the anode. Still another option can be to perform some reforming both externally and internally to the fuel cell. Reformable fuels can encompass hydrocarbonaceous materials that can be reacted with steam and/or oxygen at elevated temperature and/or pressure to produce a gaseous product that comprises hydrogen.

The basic structure of a molten carbonate fuel cell includes a cathode, an anode, and a matrix between the cathode and anode that includes one or more molten carbonate salts that serve as the electrolyte. During conventional operation of a molten carbonate fuel cell, the molten carbonate salts partially diffuse into the pores of the cathode. This diffusion of the molten carbonate salts into the pores of the cathode provides an interface region where CO₂ can be converted into CO₃ ²⁻ for transport across the electrolyte to the anode.

Conventionally, cathodes for molten carbonate fuel cells are typically constructed to have a single layer. The properties of a single layer cathode are selected based on several types of properties. First, the cathode needs to have enough structural stability to maintain the integrity of the cathode layer while also providing sufficient conductivity to allow fuel cell operation. This typically results in a use of a material such as nickel for the electrode, which is oxidized and (optionally) lithiated during initial operation of the fuel cell. With regard to other properties, it is desirable to have a pore size that is small enough to provide sufficient wetting of the cathode by the electrolyte, again to provide suitable conductivity.

One difficulty with conventional electrode materials, such as (optionally lithiated) nickel oxide, is that nickel oxide is susceptible to polarization under fuel cell operating conditions. Polarization of the cathode results in additional voltage loss across the cathode during fuel cell operation. The impact of polarization can be mitigated by increasing the operating temperature of the fuel cell, but this can lead to reduced operating lifetime. Thus it would be desirable to have a molten carbonate cathode structure that can reduce polarization, as this can provide reduced voltage loss and/or can allow for a reduced operating temperature.

U.S. Pat. No. 4,800,052 describes a method for fabricating molten carbonate fuel cell cathodes. Powders of nickel oxide and a lithium salt are pre-fired in an oxidizing atmosphere. The pre-fired powders are then formed into a cathode and sintered. The resulting cathode is described as having an improved mechanical strength.

U.S. Pat. No. 5,688,292 describes a method for fabricating molten carbonate fuel cell cathodes. The cathode is prepared from a mixture that includes nickel powder, lithium carbonate, an organic binding agent, and a low-boiling organic solvent. The organic components are removed from the cathode structure during a heating or sintering process.

U.S. Pat. No. 6,420,062 describes a dual-layer cathode for a molten carbonate fuel cell. The first layer corresponds to a lithium-activated nickel layer that is described as facing away from the electrolyte. The second layer corresponds to a cerium activated lithium cobalite layer that faces toward the electrolyte. The nickel/lithium cobalite dual-layer structure is described as generally having a higher polarization than a conventional nickel oxide cathode, although the cerium activation is described as mitigating this increased polarization.

SUMMARY

In an aspect, a method for producing electricity is provided. The method can include contacting an anode of a molten carbonate fuel cell with an anode input stream. A second cathode layer of a cathode of the molten carbonate fuel cell is contacted with a cathode inlet stream comprising O₂ and CO₂. The second cathode layer can include an average pore diameter of 5.5 μm or more. The cathode can further include a first cathode layer adjacent to an electrolyte of the fuel cell. The first cathode layer can have an average pore diameter of 4.5 μm or less. The molten carbonate fuel cell can be operated at a current density of 60 mA/cm² or more to generate electricity, an anode exhaust comprising H₂, CO, and CO₂, and a cathode exhaust comprising CO₂.

In another aspect, a method for forming a molten carbonate fuel cell is provided. The method can include depositing a first layer of first cathode precursor particles having an average particle size of 1.0 μm to 3.0 μm. A second layer comprising 1.0 vol % to 30 vol % of lithium pore-forming compound particles and 70 vol % or less of second cathode precursor particles can then be deposited. The lithium pore-forming compound particles can have an average particle size of 4.0 μm to 10 μm and/or the second cathode precursor particles having an average particle size of 1.0 μm to 3.0 μm. The first layer and the second layer can then be sintered to form a cathode. The cathode can include a first cathode layer having an average pore size of 4.5 μm or less and a second cathode layer having an average pore size of 5.5 μm or more. The first cathode precursor particles and the second cathode precursor particles optionally can have substantially the same composition.

In still another aspect, a molten carbonate fuel cell is provided. The molten carbonate fuel cell can include an anode adjacent to an anode collector. The fuel cell can further include an electrolyte matrix comprising an electrolyte. The fuel cell can further include a cathode comprising a first cathode layer adjacent to the electrolyte matrix and a second cathode layer adjacent to a cathode collector. The first cathode layer can have an average pore diameter of 4.5 μm or less. The second cathode layer can have an average pore diameter of 5.5 μm or more.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an example of a dual-layer cathode for a molten carbonate fuel cell.

FIG. 2 shows an example of a method for making a dual-layer cathode.

FIG. 3 shows an example of a portion of a molten carbonate fuel cell stack.

FIG. 4 shows a flow pattern example for a molten carbonate fuel cell with an anode flow direction that is aligned roughly perpendicular to a cathode flow direction.

FIG. 5 shows polarization values for various cathodes during operation of a molten carbonate fuel cell.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Overview

In various aspects, a layered cathode structure for a molten carbonate fuel cell is provided. The layered cathode can include at least a first cathode layer and a second cathode layer. The first cathode layer can correspond to a layer that is adjacent to the molten carbonate electrolyte during operation, while the second cathode layer can correspond to a layer that is adjacent to the cathode collector of the fuel cell. The first cathode layer can be formed by sintering a layer that includes a conventional precursor material for forming a cathode, such as nickel particles. The second cathode layer can be formed by sintering a layer that includes a mixture of particles of a conventional precursor material and 1.0 vol % to 30 vol % of particles of a lithium pore-forming compound. Optionally, the particles of the conventional precursor material in the first layer and the second layer can be the same. The inclusion of the lithium pore-forming compound in the second layer can allow the second layer to have a higher porosity than the first layer. The resulting layered cathode structure can have an increased pore size adjacent to the cathode collector to facilitate diffusion of CO₂ into the electrolyte interface, while also having a smaller pore size adjacent to the electrolyte to allow for improved electrical contact at the interface between the electrolyte and the cathode. It has been unexpectedly discovered that this layered cathode structure can provide reduced cathode polarization relative to a conventional cathode, thus reducing the resistance across the fuel cell during operation and providing a corresponding reduction in waste heat generated during operation at a given temperature. Additionally or alternately, by mitigating the polarization that occurs as the operating temperature of a fuel cell is reduced, the layered cathode can allow a fuel cell to be operated at a lower temperature while still providing a desired level of conductivity.

Conventionally, the choice of materials for molten carbonate fuel cell cathodes has been based on balancing the structural integrity of the porous cathode with providing good conductivity. Typically, this results in selection of a nickel oxide cathode, such as a cathode formed from nickel particles that are formed into the desired cathode shape and then lithiated and oxidized. When lithiated, nickel oxide provides desirable conductivity. The resulting nickel oxide cathode also has good structural stability. While the nickel oxide cathode can be slowly dissolved during fuel cell operation, materials with higher stability than nickel oxide in the molten carbonate fuel cell environment tend to have one or more properties (such as conductivity or polarization) that are less favorable.

An alternative type of cathode material can be LiFeO₂ (or Li₂MnO₃), but such cathode materials can require doping to have sufficient electric conductivity. However, even with doping, the conductivity of such materials is typically lower than lithiated NiO. Generally, an LiFeO₂ cathode may have lower electrochemical performance than lithiated NiO. However, such a cathode structure could be tailored to improve gas diffusion as one of the layers in a layered cathode design.

For nickel oxide cathodes, the typical goal of the porous structure is to provide pores of a suitable size to improve wetting by the molten carbonate. Typically this corresponds to a preference for smaller pore sizes, as conventionally it is believed that smaller pore sizes result in a larger contact area (per volume) for the electrolyte at the electrolyte interface. More generally, for a given type of cathode material, it is conventionally believed that increasing the pore size results in increased polarization.

It has been unexpectedly discovered that the pore size of the cathode in the region that is adjacent to the current collector can also impact the polarization in the cathode. Without being bound by any particular theory, it is believed that having larger pores and/or increased porosity in the portion of the cathode near the cathode collector can enhance the ability of gas to diffuse into the cathode. This benefit can be obtained even though a second portion of the cathode that is adjacent to the electrolyte has a smaller pore size. Based on this discovery, in various aspects, a dual layer (or multi-layer) cathode is described herein, along with methods for forming such a dual layer (or multi-layer) cathode. The combination of having a larger pore size near the cathode collector and a smaller pore size near the electrolyte can result in a cathode with reduced polarization.

A dual-layer cathode can provide additional benefits when operating an MCFC to have enhanced CO₂ utilization. One difficulty in using MCFCs for elevated CO₂ capture is that the operation of the fuel cell can potentially be kinetically limited if one or more of the reactants required for fuel cell operation is present in low quantities. For example, when using a cathode input stream with a CO₂ content of 4.0 vol % or less, achieving a CO₂ utilization of 75% or more corresponds to a cathode outlet concentration of 1.0 vol % or less. However, a cathode outlet concentration of 1.0 vol % or less does not necessarily mean that the CO₂ is evenly distributed throughout the cathode. Instead, the concentration will typically vary within the cathode due to a variety of factors, such as the flow patterns in the anode and the cathode. The variations in CO₂ concentration can result in portions of the cathode where CO₂ concentrations substantially below 1.0 vol % are present.

Conventional operating conditions for molten carbonate fuel cells typically correspond to conditions where the amount of alternative ion transport is reduced, minimized, or non-existent. The amount of alternative ion transport can be quantified based on the transference for a fuel cell. The transference is defined as the fraction of ions transported across the molten carbonate electrolyte that correspond to carbonate ions, as opposed to hydroxide ions and/or other ions. A convenient way to determine the transference can be based on comparing a) the measured change in CO₂ concentration at the cathode inlet versus the cathode outlet with b) the amount of carbonate ion transport required to achieve the current density being produced by the fuel cell. It is noted that this definition for the transference assumes that back-transport of CO₂ from the anode to the cathode is minimal. It is believed that such back-transport is minimal for the operating conditions described herein. For the CO₂ concentrations, the cathode input stream and/or cathode output stream can be sampled, with the sample diverted to a gas chromatograph for determination of the CO₂ content. The average current density for the fuel cell can be measured in any convenient manner.

Under conventional operating conditions, the transference can be relatively close to 1.0, such as 0.98 or more and/or such as having substantially no alternative ion transport. A transference of 0.98 or more means that 98% or more of the ionic charge transported across the electrolyte corresponds to carbonate ions. It is noted that hydroxide ions have a charge of −1 while carbonate ions have a charge of −2, so two hydroxide ions need to be transported across the electrolyte to result in the same charge transfer as transport of one carbonate ion.

In contrast to conventional operating conditions, operating a molten carbonate fuel cell with transference of 0.95 or less (or 0.97 for a fuel cell including a suitable layered cathode) can increase the effective amount of carbonate ion transport that is achieved, even though a portion of the current density generated by the fuel cell is due to transport of ions other than carbonate ions. In order to operate a fuel cell with a transference of 0.97 or less, or 0.95 or less, depletion of CO₂ has to occur within the fuel cell cathode. It has been discovered that such depletion of CO₂ within the cathode tends to be localized. As a result, many regions within a fuel cell cathode can still have sufficient CO₂ for normal operation. These regions contain additional CO₂ that would be desirable to transport across an electrolyte, such as for carbon capture. However, the CO₂ in such regions is typically not transported across the electrolyte when operating under conventional conditions. By selecting operating conditions with a transference of 0.97 or less, or 0.95 or less, the regions with sufficient CO₂ can be used to transport additional CO₂ while the depleted regions can operate based on alternative ion transport. This can increase the practical limit for the amount of CO₂ captured from a cathode input stream.

One of the advantages of transport of alternative ions across the electrolyte is that the fuel cell can continue to operate, even though a sufficient number of CO₂ molecules are not kinetically available. This can allow additional CO₂ to be transferred from cathode to anode even though the amount of CO₂ present in the cathode would conventionally be considered insufficient for normal fuel cell operation. This can allow the fuel cell to operate with a measured CO₂ utilization closer to 100%, while the calculated CO₂ utilization (based on current density) can be at least 3% greater than the measured CO₂ utilization, or at least 5% greater, or at least 10% greater, or at least 20% greater. It is noted that alternative ion transport can allow a fuel cell to operate with a current density that would correspond to more than 100% calculated CO₂ utilization.

Although transport of alternative ions can allow a fuel cell to maintain a target current density, it has further been discovered that transport of alternative ions across the electrolyte can also reduce or minimize the lifetime of a molten carbonate fuel cell. Thus, mitigation of this loss in fuel cell lifetime is desirable. It has been unexpectedly discovered that a layered cathode as described herein can reduce or minimize the amount of alternative ion transport while performing elevated CO₂ capture.

In some aspects, elevated CO₂ capture can be defined based on the amount of transference, such as a transference of 0.97 or less, or 0.95 or less, or 0.93 or less, or 0.90 or less. Maintaining an operating condition with transference of 0.97 or less can typically also result in a CO₂ concentration in the cathode output stream of 2.0 vol % or less, or 1.5 vol % or less, or 1.0 vol % or less. At higher CO₂ concentrations in the cathode output stream, there is typically not sufficient local depletion of CO₂ to result in lower transference values.

The presence of elevated CO₂ capture can also be indicated by other factors, although such other factors are by themselves typically not a sufficient condition to indicate elevated CO₂ capture. For example, when using a lower CO₂ concentration cathode input stream, elevated CO₂ capture can in some aspects correspond to a CO₂ utilization of 70% or more, or 75% or more, or 80% or more, such as up to 95% or possibly still higher. Examples of lower concentration sources of CO₂ can correspond to CO₂ sources that result in cathode input streams containing 5.0 vol % or less of CO₂, or 4.0 vol % or less, such as down to 1.5 vol % or possibly lower. The exhaust from a natural gas turbine is an example of a CO₂-containing stream that often has a CO₂ content of 5.0 vol % or less of CO₂, or 4.0 vol % or less. Additionally or alternately, elevated CO₂ capture can correspond to operating conditions where the molten carbonate fuel cell is used to generate a substantial amount of current density, such as 60 mA/cm² or more, or 80 mA/cm² or more, or 100 mA/cm² or more, or 120 mA/cm² or more, or 150 mA/cm² or more, or 200 mA/cm² or more, such as up to 300 mA/cm² or possibly still higher. It is noted that alternative ion transport can also be indicated by a reduced operating voltage for a fuel cell, as the reaction pathway for alternative ion transport has a lower theoretical voltage than the reaction pathway that uses carbonate ions.

Conventionally, the CO₂ concentration in the cathode exhaust of a molten carbonate fuel cell is maintained at a relatively high value, such as 5 vol % CO₂ or more, or 10 vol % CO₂ or more, or possibly still higher. Additionally, molten carbonate fuel cells are typically operated at CO₂ utilization values of 70% or less. When either of these conditions are present, the dominant mechanism for transport of charge across the molten carbonate electrolyte is transport of carbonate ions. While it is possible that transport of alternative ions (such as hydroxide ions) across the electrolyte occurs under such conventional conditions, the amount of alternative ion transport is de minimis, corresponding to 2% or less of the current density (or equivalently, a transference of 0.98 or more).

As an alternative to describing operating conditions in terms of transference, the operating conditions can be described based on measured CO₂ utilization and “calculated” CO₂ utilization based on average current density. In this discussion, the measured CO₂ utilization corresponds to the amount of CO₂ that is removed from the cathode input stream. This can be determined, for example, by using gas chromatography to determine the CO₂ concentration in the cathode input stream and the cathode output stream. This can also be referred to as the actual CO₂ utilization, or simply as the CO₂ utilization. In this discussion, the calculated CO₂ utilization is defined as the CO₂ utilization that would occur if all of the current density generated by the fuel cell was generated based on transport of CO₃ ²⁻ ions across the electrolyte (i.e., transport of ions based on CO₂). The difference in measured CO₂ utilization and the calculated CO₂ utilization can be used individually to characterize the amount of alternative ion transport and/or these values can be used to calculate the transference, as described above.

In some aspects, any convenient type of electrolyte suitable for operation of a molten carbonate fuel cell can be used. Many conventional MCFCs use a eutectic carbonate mixture as the carbonate electrolyte, such as a eutectic mixture of 62 mol % lithium carbonate and 38 mol % potassium carbonate (62% Li₂CO₃/38% K₂CO₃) or a eutectic mixture of 52 mol % lithium carbonate and 48 mol % sodium carbonate (52% Li₂CO₃/48% Na₂CO₃). Other eutectic mixtures are also available, such as a eutectic mixture of 40 mol % lithium carbonate and 60 mol % potassium carbonate (40% Li₂CO₃/60% K₂CO₃). While eutectic mixtures of carbonates can be convenient as an electrolyte for various reasons, non-eutectic mixtures of carbonates can also be suitable. Generally, such non-eutectic mixtures can include various combinations of lithium carbonate, sodium carbonate, and/or potassium carbonate. Optionally, lesser amounts of other metal carbonates can be included in the electrolyte as additives, such as other alkali carbonates (rubidium carbonate, cesium carbonate), or other types of metal carbonates such as barium carbonate, bismuth carbonate, lanthanum carbonate, or tantalum carbonate.

In this discussion, the average pore diameter for a cathode layer can be determined using a mercury porosimetry technique, such as ASTM D4284. In this discussion, the average particle size for powders used to form the layers of a cathode structure can be determined by any laser scattering particle size distribution analyzer available commercially such as Horriba LA-950. Optionally, such particle size characterization can be performed according to ASTM D4464.

Formation of Dual-Layer Cathode

In various aspects, a dual-layer cathode with larger pore sizes in the layer adjacent to the cathode collector and smaller pore sizes in the layer adjacent to the electrolyte can be formed using appropriate precursor materials, such as nickel particles and lithium carbonate particles.

An example of a suitable material for forming the smaller pore size layer (preferably the first layer, or the layer adjacent to the electrolyte) is nickel particles, such as nickel filamentary particles. Other examples of suitable cathode precursor compounds include LiFeO₂ particles, La_(0.8)Sr_(0.2)CoO₃ particles, or other typical particles for cathode formation. The particles can have an average particle size of roughly 1.0 μm to 3.0 μm. The nickel particles (or other particles) can be formed into the layer by any method typically used for cathode formation, such as powder deposition and dry doctoring/spreading, tape casting, spray coating, screen printing, or another convenient method. When sintering is performed, the sintering can be performed by heating the assembled molten carbonate fuel cell structure to typical fuel cell operating conditions. Prior to sintering, the first layer can have a porosity of 70%% to 80%, or 72% to 77%. After sintering to convert the first layer to nickel oxide, the average pore size of the first cathode layer can be 4.5 μm or less, or 1.0 μm to 4.5 μm, or 3.0 μm to 4.5 μm, or 1.0 μm to 4.5 μm, or 3.0 μm to 4.0 μm. The porosity after sintering to form nickel oxide can be 50% to 62%, or 52% to 61%. The first cathode layer can have a layer thickness of roughly 250 μm to 400 μm (roughly 10 mil to 15 mil).

Examples of suitable materials for the second layer (or layer adjacent to the cathode collector) include homogenous mixtures of the particles from the first layer with lithium-containing particles that act as pore-forming compounds. The lithium pore-forming particles can correspond to lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, or another convenient lithium compound that is a solid at room temperature but can form a molten phase during the sintering of the cathode at conditions similar to the fuel cell operating conditions. The particle size for the lithium pore-forming particles can also be roughly 4.0 μm to 10 μm. The second layer can also be formed by any convenient method, such as powder deposition and dry doctoring/spreading, tape casting, spray coating, screen printing or another convenient method. The amount of lithium pore-forming compound used in the second layer can correspond to 1.0 vol % to 30 vol % of the second layer. Prior to sintering, the second layer can have a porosity of 78%% to 88%, or 80% to 87%. After sintering to convert the second layer to a nickel oxide, the average pore size of the second cathode layer can be 5.5 μm or more, or 5.5 μm-10.0 μm, or 6.0 μm-10.0 μm, or 6.0-8.0 μm, or 7.0 μm-9.0 μm, or 7.0 μm-8.0 μm. The porosity after sintering to form nickel oxide can be 65% to 77%, or 66% to 76%. The second cathode layer can have a thickness of roughly 500 μm to 800 μm (roughly 20 mil to 30 mil).

Use of a lithium pore-forming compound particle can provide a variety of advantages. In addition to serving as a pore-forming agent, the lithium compound can also provide lithium for forming a lithiated nickel oxide in the cathode. This can reduce or minimize the amount of the electrolyte that is consumed by the nickel oxide in the cathode during initial operation of the fuel cell. Additionally, a lithium pore-forming compound can convert to a molten state at a sufficiently high temperature (450° C. or more, or 490° C. or more) so that the resulting pore structure formed in the nickel oxide is stable. Attempts to use sacrificial pore-forming agents, such as plastic beads or carbon particles, can tend to result in pore structures that collapse due to lack of structural integrity. Such sacrificial pore-forming agents tend to thermally decompose or combust at temperatures of 300° C.-400° C. or lower. At such temperatures, the nickel oxide is not sufficiently sintered to stabilize the pore network. Another alternative for creating a pore network with larger pore sizes can be to pack nickel particles at lower density. However, during the sintering process, layers with initially lower densities can tend to result in undesirable amounts of cathode shrinkage.

In some aspects, the cathode precursor compound(s) used to form the first cathode layer can be substantially the same as the cathode precursor compound(s) that are mixed with the lithium pore-forming compound to form the second cathode layer. For example, in some aspects, 70 wt % or more of the cathode precursor compounds used to form the second cathode layer can have substantially the same composition as the cathode precursor compounds used to form the first cathode layer. In other words, if nickel particles are used as the cathode precursor compound to form the first cathode layer, then 70 wt % or more (or 90 wt % or more, or 95 wt % or more) of the cathode precursor compounds used to form the second cathode layer can be nickel oxide particles. When 95 wt % or more of the cathode precursor compounds used to form the first cathode layer and the second cathode layer are the same, the resulting cathode layers are defined as having substantially the same composition. It is noted that the lithium pore forming compounds are not cathode precursor compounds under the definition provided herein.

FIG. 1 shows schematic examples of a dual layer structure as initially formed (top schematic 101) and after sintering to produce the final cathode structure (bottom schematic 102). The example shown in FIG. 1 is described here with regard to formation of a nickel oxide cathode, but any other convenient type of cathode could be formed. In the example shown in FIG. 1 , the dual-layer structure prior to sintering includes a cathode collector 160, a first layer 174, a second layer 176, and an electrolyte matrix 140 that includes electrolyte 142. As shown in FIG. 1 , the second layer includes lithium carbonate particles as pore-forming particles 179. After sintering, the cathode structure 102 is formed. Sintering converts second layer 176 which includes nickel particles and lithium carbonate particles into second cathode layer 156 which includes lithiated nickel oxide. During sintering, the lithium carbonate particles melt and assist with lithiation of the nickel oxide. The melting of the lithium carbonate particles assists with formation of larger pores 159 in the pore structure of the second cathode layer 156. Sintering also converts first layer 174 into first cathode layer 154 which includes lithiated nickel oxide, with the lithium being provided either by the lithium carbonate or by lithium from electrolyte 142.

FIG. 2 shows an example of a method for making a dual-layer cathode structure. In FIG. 2 , the process for forming the cathode begins by depositing a first layer using a first source of Ni particles 210. Optionally, the first layer can be deposited on an electrolyte matrix structure, as part of a larger manufacturing process for forming a complete molten carbonate fuel cell. The first layer can be leveled using a first leveling blade 220. A second layer can then be deposited using a second source 230 that includes a homogenous mixture of Ni particles and lithium carbonate particles. The second layer can then be leveled using a second leveling knife 240. Rollers 250 can then be used to compact the first layer and second layer to a desired thickness.

Conditions for Molten Carbonate Fuel Operation with Alternative Ion Transport

In various aspects, the operating conditions for a molten carbonate fuel cell (such as a cell as part of a fuel cell stack) can be selected to correspond to a transference of 0.97 or less, thereby causing the cell to transport both carbonate ion and at least one type of alternative ion across the electrolyte. In addition to transference, operating conditions that can indicate that a molten carbonate fuel cell is operating with transport of alternative ions include, but are not limited to, CO₂ concentration for the cathode input stream, the CO₂ utilization in the cathode, the current density for the fuel cell, the voltage drop across the cathode, the voltage drop across the anode, and the O₂ concentration in the cathode input stream. Additionally, the anode input stream and fuel utilization in the anode can be generally selected to provide the desired current density.

Generally, to cause alternative ion transport, the CO₂ concentration in at least a portion of the cathode needs to be sufficiently low while operating the fuel cell to provide a sufficiently high current density. Having a sufficiently low CO₂ concentration in the cathode typically corresponds to some combination of a low CO₂ concentration in the cathode input flow, a high CO₂ utilization, and/or a high average current density. However, such conditions alone are not sufficient to indicate a transference of 0.97 or less, or 0.95 or less.

For example, a molten carbonate fuel cell with a cathode open area of roughly 33% was operated with a CO₂ cathode inlet concentration of 19 vol %, 75% CO₂ utilization, and 160 mA/cm² of average current density. These conditions corresponded to a difference between calculated CO₂ utilization and measured CO₂ utilization of less than 1%. Thus, the presence of substantial alternative ion transport/a transference of 0.97 or less, or 0.95 or less, cannot be inferred simply from the presence of a high CO₂ utilization and a high average current density.

As another example, a molten carbonate fuel cell with a cathode open area of between 50% and 60% was operated with a CO₂ cathode inlet concentration of 4.0 vol %, 89% CO₂ utilization, and 100 mA/cm² of current density. These conditions corresponded to a transference of at least 0.97. Thus, the presence of a transference of 0.95 or less/substantial alternative ion transport cannot be inferred simply from the presence of high CO₂ utilization in combination with low CO₂ concentration in the cathode input stream.

As still another example, a molten carbonate fuel cell with a cathode open area of between 50% and 60% was operated with a CO₂ cathode inlet concentration of 13 vol %, 68% CO₂ utilization, and 100 mA/cm² of current density. These conditions corresponded to a transference of at least 0.98.

In this discussion, operating an MCFC to transport alternative ions across the electrolyte is defined as operating the MCFC so that more than a de minimis amount of alternative ions are transported. It is possible that minor amounts of alternative ions are transported across an MCFC electrolyte under a variety of conventional conditions. Such alternative ion transport under conventional conditions can correspond to a transference of 0.98 or more, which corresponds to transport of alternative ions corresponding to less than 2.0% of the current density for the fuel cell.

In this discussion, operating an MCFC to cause alternative ion transport is defined as operating an MCFC with a transference of 0.95 or less, so that 5.0% or more of the current density (or, 5.0% or more of the calculated CO₂ utilization) corresponds to current density based on transport of alternative ions, or 10% or more, or 20% or more, such as up to 35% or possibly still higher. It is noted that in some aspects, operating with a layered cathode as described herein can reduce or minimize the amount of alternative ion transport under conditions that would otherwise result in a transference of 0.95 or less, so that some operating conditions with elevated CO₂ capture/substantial alternative ion transport may correspond to a transference of 0.97 or less.

In this discussion, operating an MCFC to cause substantial alternative ion transport (i.e., to operate with a transference of 0.95 or less, or 0.97 or less with increased open area and/or reduced unblocked flow cross-section) is further defined to correspond to operating an MCFC with voltage drops across the anode and cathode that are suitable for power generation. The total electrochemical potential difference for the reactions in a molten carbonate fuel cell is ˜1.04 V. Due to practical considerations, an MCFC is typically operated to generate current at a voltage near 0.7 V or about 0.8 V. This corresponds to a combined voltage drop across the cathode, electrolyte, and anode of roughly 0.34 V. In order to maintain stable operation, the combined voltage drop across the cathode, electrolyte, and anode can be less than −0.5 V, so that the resulting current generated by the fuel cell is at a voltage of 0.55 V or more, or 0.6 V or more.

With regard to the anode, one condition for operating with substantial alternative ion transport can be to have an H₂ concentration of 8.0 vol % or more, or 10 vol % or more in the region where the substantial alternative ion transport occurs. Depending on the aspect, this could correspond to a region near the anode inlet, a region near the cathode outlet, or a combination thereof. Generally, if the H₂ concentration in a region of the anode is too low, there will be insufficient driving force to generate substantial alternative ion transport.

Suitable conditions for the anode can also include providing the anode with H₂, a reformable fuel, or a combination thereof; and operating with any convenient fuel utilization that generates a desired current density, including fuel utilizations ranging from 20% to 80%. In some aspects this can correspond to a traditional fuel utilization amount, such as a fuel utilization of 60% or more, or 70% or more, such as up to 85% or possibly still higher. In other aspects, this can correspond to a fuel utilization selected to provide an anode output stream with an elevated content of H₂ and/or an elevated combined content of H₂ and CO (i.e., syngas), such as a fuel utilization of 55% or less, or 50% or less, or 40% or less, such as down to 20% or possibly still lower. The H₂ content in the anode output stream and/or the combined content of H₂ and CO in the anode output stream can be sufficient to allow generation of a desired current density. In some aspects, the H₂ content in the anode output stream can be 3.0 vol % or more, or 5.0 vol % or more, or 8.0 vol % or more, such as up to 15 vol % or possibly still higher. Additionally or alternately, the combined amount of H₂ and CO in the anode output stream can be 4.0 vol % or more, or 6.0 vol % or more, or 10 vol % or more, such as up to 20 vol % or possibly still higher. Optionally, when the fuel cell is operated with low fuel utilization, the H₂ content in the anode output stream can be in a higher range, such as an H₂ content of 10 vol % to 25 vol %. In such aspects, the syngas content of the anode output stream can be correspondingly higher, such as a combined H₂ and CO content of 15 vol % to 35 vol %. Depending on the aspect, the anode can be operated to increase the amount of electrical energy generated, to increase the amount of chemical energy generated (i.e., H₂ generated by reforming that is available in the anode output stream), or operated using any other convenient strategy that is compatible with operating the fuel cell to cause alternative ion transport.

In addition to having sufficient H₂ concentration in the anode, one or more locations within the cathode need to have a low enough CO₂ concentration so that the more favorable pathway of carbonate ion transport is not readily available. In some aspects, this can correspond to a having a CO₂ concentration in the cathode outlet stream (i.e., cathode exhaust) of 2.0 vol % or less, or 1.0 vol % or less, or 0.8 vol % or less. It is noted that due to variations within the cathode, an average concentration of 2.0 vol % or less (or 1.0 vol % or less, or 0.8 vol % or less) in the cathode exhaust can correspond to a still lower CO₂ concentration in localized regions of the cathode. For example, in a cross-flow configuration, at a corner of the fuel cell that is adjacent to the anode inlet and the cathode outlet, the CO₂ concentration can be lower than a corner of the same fuel cell that is adjacent to the anode outlet and the cathode outlet. Similar localized variations in CO₂ concentration can also occur in fuel cells having a co-current or counter-current configuration.

In addition to having a low concentration of CO₂, the localized region of the cathode can also have 1.0 vol % or more of O₂, or 2.0 vol % or more. In the fuel cell, O₂ is used to form the hydroxide ion that allows for alternative ion transport. If sufficient O₂ is not present, the fuel cell will not operate as both the carbonate ion transport and alternative ion transport mechanisms are dependent on O₂ availability. With regard to O₂ in the cathode input stream, in some aspects this can correspond to an oxygen content of 4.0 vol % to 15 vol %, or 6.0 vol % to 10 vol %.

It has been observed that a sufficient amount of water should also be present for alternative ion transport to occur, such as 1.0 vol % or more, or 2.0 vol % or more. Without being bound by any particular theory, if water is not available in the cathode when attempting to operate with substantial alternative ion transport, the fuel cell appears to degrade at a much more rapid rate than the deactivation rate that is observed due to alternative ion transport with sufficient water available. It is noted that because air is commonly used as an O₂ source, and since H₂O is one of the products generated during combustion, a sufficient amount of water is typically available within the cathode.

Due to the non-uniform distribution of cathode gas and/or anode gas during operation of a molten carbonate fuel cell for elevated CO₂ capture, it is believed that one or more of the corners and/or edges of the molten carbonate fuel cell will typically have a substantially higher density of alternative ion transport. The one or more corners can correspond to locations where the CO₂ concentration in the cathode is lower than average, or a location where the H₂ concentration in the anode is greater than average, or a combination thereof.

In this discussion, a fuel cell can correspond to a single cell, with an anode and a cathode separated by an electrolyte. The anode and cathode can receive input gas flows to facilitate the respective anode and cathode reactions for transporting charge across the electrolyte and generating electricity. A fuel cell stack can represent a plurality of cells in an integrated unit. Although a fuel cell stack can include multiple fuel cells, the fuel cells can typically be connected in parallel and can function (approximately) as if they collectively represented a single fuel cell of a larger size. When an input flow is delivered to the anode or cathode of a fuel cell stack, the fuel stack can include flow channels for dividing the input flow between each of the cells in the stack and flow channels for combining the output flows from the individual cells. In this discussion, a fuel cell array can be used to refer to a plurality of fuel cells (such as a plurality of fuel cell stacks) that are arranged in series, in parallel, or in any other convenient manner (e.g., in a combination of series and parallel). A fuel cell array can include one or more stages of fuel cells and/or fuel cell stacks, where the anode/cathode output from a first stage may serve as the anode/cathode input for a second stage. It is noted that the anodes in a fuel cell array do not have to be connected in the same way as the cathodes in the array. For convenience, the input to the first anode stage of a fuel cell array may be referred to as the anode input for the array, and the input to the first cathode stage of the fuel cell array may be referred to as the cathode input to the array. Similarly, the output from the final anode/cathode stage may be referred to as the anode/cathode output from the array. In aspects where a fuel cell stack includes separate reforming elements, it is noted that the anode input flow may first pass through a reforming element prior to entering one or more anodes associated with the reforming element.

It should be understood that reference to use of a fuel cell herein typically denotes a “fuel cell stack” composed of individual fuel cells, and more generally refers to use of one or more fuel cell stacks in fluid communication. Individual fuel cell elements (plates) can typically be “stacked” together in a rectangular array called a “fuel cell stack”. Additional types of elements can also be included in the fuel cell stack, such as reforming elements. This fuel cell stack can typically take a feed stream and distribute reactants among all of the individual fuel cell elements and can then collect the products from each of these elements. When viewed as a unit, the fuel cell stack in operation can be taken as a whole even though composed of many (often tens or hundreds) of individual fuel cell elements. These individual fuel cell elements can typically have similar voltages (as the reactant and product concentrations are similar), and the total power output can result from the summation of all of the electrical currents in all of the cell elements, when the elements are electrically connected in series. Stacks can also be arranged in a series arrangement to produce high voltages. A parallel arrangement can boost the current. If a sufficiently large volume fuel cell stack is available to process a given exhaust flow, the systems and methods described herein can be used with a single molten carbonate fuel cell stack. In other aspects of the invention, a plurality of fuel cell stacks may be desirable or needed for a variety of reasons.

For the purposes of this invention, unless otherwise specified, the term “fuel cell” should be understood to also refer to and/or is defined as including a reference to a fuel cell stack composed of a set of one or more individual fuel cell elements for which there is a single input and output, as that is the manner in which fuel cells are typically employed in practice. Similarly, the term fuel cells (plural), unless otherwise specified, should be understood to also refer to and/or is defined as including a plurality of separate fuel cell stacks. In other words, all references within this document, unless specifically noted, can refer interchangeably to the operation of a fuel cell stack as a “fuel cell.” For example, the volume of exhaust generated by a commercial scale combustion generator may be too large for processing by a fuel cell (i.e., a single stack) of conventional size. In order to process the full exhaust, a plurality of fuel cells (i.e., two or more separate fuel cells or fuel cell stacks) can be arranged in parallel, so that each fuel cell can process (roughly) an equal portion of the combustion exhaust. Although multiple fuel cells can be used, each fuel cell can typically be operated in a generally similar manner, given its (roughly) equal portion of the combustion exhaust.

Example of Molten Carbonate Fuel Cell Operation: Cross Flow Orientation for Cathode and Anode

FIG. 3 shows a general example of a portion of a molten carbonate fuel cell stack. The portion of the stack shown in FIG. 3 corresponds to a fuel cell 301. In order to isolate the fuel cell from adjacent fuel cells in the stack and/or other elements in the stack, the fuel cell includes separator plates 310 and 311. In FIG. 3 , the fuel cell 301 includes an anode 330 and a cathode 350 that are separated by an electrolyte matrix 340 that contains an electrolyte 342. In various aspects, cathode 350 can correspond to a dual-layer (or multi-layer) cathode. Anode collector 320 provides electrical contact between anode 330 and the other anodes in the stack, while cathode collector 360 provides similar electrical contact between cathode 350 and the other cathodes in the fuel cell stack. Additionally anode collector 320 allows for introduction and exhaust of gases from anode 330, while cathode collector 360 allows for introduction and exhaust of gases from cathode 350.

During operation, CO₂ is passed into the cathode collector 360 along with O₂. The CO₂ and O₂ diffuse into the porous cathode 350 and travel to a cathode interface region near the boundary of cathode 350 and electrolyte matrix 340. In the cathode interface region, a portion of electrolyte 342 can be present in the pores of cathode 350. The CO₂ and O₂ can be converted near/in the cathode interface region to carbonate ion (CO₃ ²⁻), which can then be transported across electrolyte 342 (and therefore across electrolyte matrix 340) to facilitate generation of electrical current. In aspects where alternative ion transport is occurring, a portion of the O₂ can be converted to an alternative ion, such as a hydroxide ion or a peroxide ion, for transport in electrolyte 342. After transport across the electrolyte 342, the carbonate ion (or alternative ion) can reach an anode interface region near the boundary of electrolyte matrix 340 and anode 330. The carbonate ion can be converted back to CO₂ and H₂O in the presence of H₂, releasing electrons that are used to form the current generated by the fuel cell. The H₂ and/or a hydrocarbon suitable for forming H₂ are introduced into anode 330 via anode collector 320.

The flow direction within the anode of a molten carbonate fuel cell can have any convenient orientation relative to the flow direction within a cathode. One option can be to use a cross-flow configuration, so that the flow direction within the anode is roughly at a 90° angle relative to the flow direction within the cathode. This type of flow configuration can have practical benefits, as using a cross-flow configuration can allow the manifolds and/or piping for the anode inlets/outlets to be located on different sides of a fuel cell stack from the manifolds and/or piping for the cathode inlets/outlets.

FIG. 4 schematically shows an example of a top view for a fuel cell cathode, along with arrows indicating the direction of flow within the fuel cell cathode and the corresponding fuel cell anode. In FIG. 4 , arrow 405 indicates the direction of flow within cathode 450, while arrow 425 indicates the direction of flow with the anode (not shown).

Because the anode and cathode flows are oriented at roughly 90° relative to each other, the anode and cathode flow patterns can contribute to having different reaction conditions in various parts of the cathode. The different conditions can be illustrated by considering the reaction conditions in the four corners of the cathode. In the illustration in FIG. 4 , the reaction conditions described herein are qualitatively similar to the reaction conditions for a fuel cell operating with a CO₂ utilization of 75% or more (or 80% or more).

Corner 482 corresponds to a portion of the fuel cell that is close to the entry point for both the cathode input flow and the anode input flow. As a result, the concentration of both CO₂ (in the cathode) and H₂ (in the anode) is relatively high in corner 482. Based on the high concentrations, it is expected that portions of the fuel cell near corner 482 can operate under expected conditions, with substantially no transport of ions other than carbonate ions across the electrolyte.

Corner 484 corresponds to a portion of the fuel cell that is close to the entry point for the cathode input flow and close to the exit point for the anode output flow. In locations near corner 484, the amount of current density may be limited due to the reduced concentration of H₂ in the anode, depending on the fuel utilization. However, sufficient CO₂ should be present that any ions transported across the electrolyte substantially correspond to carbonate ions.

Corner 486 corresponds to a portion of the fuel cell that is close to the exit point for the anode output flow and close to the exit point for the cathode output flow. In locations near corner 486, due to the lower concentrations of both H₂ (in the anode) and CO₂ (in the cathode), little or no current would be expected due to the low driving force for the fuel cell reaction.

Corner 488 corresponds to a portion of the fuel cell that is close to the entry point for the anode input flow and close to the exit point for the cathode output flow. The relatively high availability of hydrogen at locations near corner 488 would be expected to result in substantial current density. However, due to the relatively low concentration of CO₂, a substantial amount of transport of hydroxide ions and/or other alternative ions can occur. Depending on the aspect, the substantial amount of alternative ion transport can increase the calculated CO₂ utilization by 5% or more, or 10% or more, or 15% or more, or 20% or more. Additionally or alternately, the transference can be 0.97 or less, or 0.95 or less, or 0.90 or less, or 0.85 or less, or 0.80 or less. The transport of substantial amounts of alternative ions across the electrolyte can temporarily allow higher current densities to be maintained at locations near corner 488. However, the transport of alternative ions can also degrade the cathode and/or anode structures, resulting in lower (and possibly no) current density over time at locations near corner 488. It is noted that at lower amounts of alternative ion transport (such as a transference of 0.96 or more, or 0.98 or more), the amount of lifetime degradation is not as severe.

It has been discovered that when alternative ion transport becomes significant at one or more locations within the fuel cell, the fuel cell will quickly begin to degrade. This is believed to be due to the one or more locations degrading and not providing any further current density. As a region(s) stops contributing to the desired current density, the remaining locations in the fuel cell have to operate at higher current densities in order to maintain a constant overall (average) current density for the fuel cell. This can cause the region for transport of alternative ions to grow, resulting in an expanding portion of the fuel cell that degrades and eventually stops working. Alternatively, degradation of a portion of the fuel cell can result in reduced total current density from the cell, which is also undesirable. A fuel cell including a layered cathode can reduce the amount of alternative ion transport that occurs during elevated CO₂ capture, allowing for longer fuel cell lifetimes.

Anode Inputs and Outputs

In various aspects, the anode input stream for a MCFC can include hydrogen, a hydrocarbon such as methane, a hydrocarbonaceous or hydrocarbon-like compound that may contain heteroatoms different from C and H, or a combination thereof. The source of the hydrogen/hydrocarbon/hydrocarbon-like compounds can be referred to as a fuel source. In some aspects, most of the methane (or other hydrocarbon, hydrocarbonaceous, or hydrocarbon-like compound) fed to the anode can typically be fresh methane. In this description, a fresh fuel such as fresh methane refers to a fuel that is not recycled from another fuel cell process. For example, methane recycled from the anode outlet stream back to the anode inlet may not be considered “fresh” methane, and can instead be described as reclaimed methane.

The fuel source used can be shared with other components, such as a turbine that uses a portion of the fuel source to provide a CO₂-containing stream for the cathode input. The fuel source input can include water in a proportion to the fuel appropriate for reforming the hydrocarbon (or hydrocarbon-like) compound in the reforming section that generates hydrogen. For example, if methane is the fuel input for reforming to generate H₂, the molar ratio of water to fuel can be from about one to one to about ten to one, such as at least about two to one. A ratio of four to one or greater is typical for external reforming, but lower values can be typical for internal reforming. To the degree that H₂ is a portion of the fuel source, in some optional aspects no additional water may be needed in the fuel, as the oxidation of H₂ at the anode can tend to produce H₂O that can be used for reforming the fuel. The fuel source can also optionally contain components incidental to the fuel source (e.g., a natural gas feed can contain some content of CO₂ as an additional component). For example, a natural gas feed can contain CO₂, N₂, and/or other inert (noble) gases as additional components. Optionally, in some aspects the fuel source may also contain CO, such as CO from a recycled portion of the anode exhaust. An additional or alternate potential source for CO in the fuel into a fuel cell assembly can be CO generated by steam reforming of a hydrocarbon fuel performed on the fuel prior to entering the fuel cell assembly.

More generally, a variety of types of fuel streams may be suitable for use as an anode input stream for the anode of a molten carbonate fuel cell. Some fuel streams can correspond to streams containing hydrocarbons and/or hydrocarbon-like compounds that may also include heteroatoms different from C and H. In this discussion, unless otherwise specified, a reference to a fuel stream containing hydrocarbons for an MCFC anode is defined to include fuel streams containing such hydrocarbon-like compounds. Examples of hydrocarbon (including hydrocarbon-like) fuel streams include natural gas, streams containing C1-C4 carbon compounds (such as methane or ethane), and streams containing heavier C5+ hydrocarbons (including hydrocarbon-like compounds), as well as combinations thereof. Still other additional or alternate examples of potential fuel streams for use in an anode input can include biogas-type streams, such as methane produced from natural (biological) decomposition of organic material.

In some aspects, a molten carbonate fuel cell can be used to process an input fuel stream, such as a natural gas and/or hydrocarbon stream, with a low energy content due to the presence of diluent compounds. For example, some sources of methane and/or natural gas are sources that can include substantial amounts of either CO₂ or other inert molecules, such as nitrogen, argon, or helium. Due to the presence of elevated amounts of CO₂ and/or inerts, the energy content of a fuel stream based on the source can be reduced. Using a low energy content fuel for a combustion reaction (such as for powering a combustion-powered turbine) can pose difficulties. However, a molten carbonate fuel cell can generate power based on a low energy content fuel source with a reduced or minimal impact on the efficiency of the fuel cell. The presence of additional gas volume can require additional heat for raising the temperature of the fuel to the temperature for reforming and/or the anode reaction. Additionally, due to the equilibrium nature of the water gas shift reaction within a fuel cell anode, the presence of additional CO₂ can have an impact on the relative amounts of H₂ and CO present in the anode output. However, the inert compounds otherwise can have only a minimal direct impact on the reforming and anode reactions. The amount of CO₂ and/or inert compounds in a fuel stream for a molten carbonate fuel cell, when present, can be at least about 1 vol %, such as at least about 2 vol %, or at least about 5 vol %, or at least about 10 vol %, or at least about 15 vol %, or at least about 20 vol %, or at least about 25 vol %, or at least about 30 vol %, or at least about 35 vol %, or at least about 40 vol %, or at least about 45 vol %, or at least about 50 vol %, or at least about 75 vol %. Additionally or alternately, the amount of CO₂ and/or inert compounds in a fuel stream for a molten carbonate fuel cell can be about 90 vol % or less, such as about 75 vol % or less, or about 60 vol % or less, or about 50 vol % or less, or about 40 vol % or less, or about 35 vol % or less.

Yet other examples of potential sources for an anode input stream can correspond to refinery and/or other industrial process output streams. For example, coking is a common process in many refineries for converting heavier compounds to lower boiling ranges. Coking typically produces an off-gas containing a variety of compounds that are gases at room temperature, including CO and various C₁-C₄ hydrocarbons. This off-gas can be used as at least a portion of an anode input stream. Other refinery off-gas streams can additionally or alternately be suitable for inclusion in an anode input stream, such as light ends (C₁-C₄) generated during cracking or other refinery processes. Still other suitable refinery streams can additionally or alternately include refinery streams containing CO or CO₂ that also contain H₂ and/or reformable fuel compounds.

Still other potential sources for an anode input can additionally or alternately include streams with increased water content. For example, an ethanol output stream from an ethanol plant (or another type of fermentation process) can include a substantial portion of H₂O prior to final distillation. Such H₂O can typically cause only minimal impact on the operation of a fuel cell. Thus, a fermentation mixture of alcohol (or other fermentation product) and water can be used as at least a portion of an anode input stream.

Biogas, or digester gas, is another additional or alternate potential source for an anode input. Biogas may primarily comprise methane and CO₂ and is typically produced by the breakdown or digestion of organic matter. Anaerobic bacteria may be used to digest the organic matter and produce the biogas. Impurities, such as sulfur-containing compounds, may be removed from the biogas prior to use as an anode input.

The output stream from an MCFC anode can include H₂O, CO₂, CO, and H₂. Optionally, the anode output stream could also have unreacted fuel (such as H₂ or CH₄) or inert compounds in the feed as additional output components. Instead of using this output stream as a fuel source to provide heat for a reforming reaction or as a combustion fuel for heating the cell, one or more separations can be performed on the anode output stream to separate the CO₂ from the components with potential value as inputs to another process, such as H₂ or CO. The H₂ and/or CO can be used as a syngas for chemical synthesis, as a source of hydrogen for chemical reaction, and/or as a fuel with reduced greenhouse gas emissions.

Cathode Inputs and Outputs

Conventionally, a molten carbonate fuel cell can be operated based on drawing a desired load while consuming some portion of the fuel in the fuel stream delivered to the anode. The voltage of the fuel cell can then be determined by the load, fuel input to the anode, air and CO₂ provided to the cathode, and the internal resistances of the fuel cell. The CO₂ to the cathode can be conventionally provided in part by using the anode exhaust as at least a part of the cathode input stream. By contrast, the present invention can use separate/different sources for the anode input and cathode input. By removing any direct link between the composition of the anode input flow and the cathode input flow, additional options become available for operating the fuel cell, such as to generate excess synthesis gas, to improve capture of carbon dioxide, and/or to improve the total efficiency (electrical plus chemical power) of the fuel cell, among others.

In various aspects, an MCFC can be operated to cause alternative ion transport across the electrolyte for the fuel cell. In order to cause alternative ion transport, the CO₂ content of the cathode input stream can be 5.0 vol % or less, or 4.0 vol % or less, such as 1.5 vol % to 5.0 vol %, or 1.5 vol % to 4.0 vol %, or 2.0 vol % to 5.0 vol %, or 2.0 vol % to 4.0 vol %.

One example of a suitable CO₂-containing stream for use as a cathode input flow can be an output or exhaust flow from a combustion source. Examples of combustion sources include, but are not limited to, sources based on combustion of natural gas, combustion of coal, and/or combustion of other hydrocarbon-type fuels (including biologically derived fuels). Additional or alternate sources can include other types of boilers, fired heaters, furnaces, and/or other types of devices that burn carbon-containing fuels in order to heat another substance (such as water or air).

Other potential sources for a cathode input stream can additionally or alternately include sources of bio-produced CO₂. This can include, for example, CO₂ generated during processing of bio-derived compounds, such as CO₂ generated during ethanol production. An additional or alternate example can include CO₂ generated by combustion of a bio-produced fuel, such as combustion of lignocellulose. Still other additional or alternate potential CO₂ sources can correspond to output or exhaust streams from various industrial processes, such as CO₂-containing streams generated by plants for manufacture of steel, cement, and/or paper.

Yet another additional or alternate potential source of CO₂ can be CO₂-containing streams from a fuel cell. The CO₂-containing stream from a fuel cell can correspond to a cathode output stream from a different fuel cell, an anode output stream from a different fuel cell, a recycle stream from the cathode output to the cathode input of a fuel cell, and/or a recycle stream from an anode output to a cathode input of a fuel cell. For example, an MCFC operated in standalone mode under conventional conditions can generate a cathode exhaust with a CO₂ concentration of at least about 5 vol %. Such a CO₂-containing cathode exhaust could be used as a cathode input for an MCFC operated according to an aspect of the invention. More generally, other types of fuel cells that generate a CO₂ output from the cathode exhaust can additionally or alternately be used, as well as other types of CO₂-containing streams not generated by a “combustion” reaction and/or by a combustion-powered generator. Optionally but preferably, a CO₂-containing stream from another fuel cell can be from another molten carbonate fuel cell. For example, for molten carbonate fuel cells connected in series with respect to the cathodes, the output from the cathode for a first molten carbonate fuel cell can be used as the input to the cathode for a second molten carbonate fuel cell.

In addition to CO₂, a cathode input stream can include O₂ to provide the components necessary for the cathode reaction. Some cathode input streams can be based on having air as a component. For example, a combustion exhaust stream can be formed by combusting a hydrocarbon fuel in the presence of air. Such a combustion exhaust stream, or another type of cathode input stream having an oxygen content based on inclusion of air, can have an oxygen content of about 20 vol % or less, such as about 15 vol % or less, or about 10 vol % or less. Additionally or alternately, the oxygen content of the cathode input stream can be at least about 4 vol %, such as at least about 6 vol %, or at least about 8 vol %. More generally, a cathode input stream can have a suitable content of oxygen for performing the cathode reaction. In some aspects, this can correspond to an oxygen content of about 5 vol % to about 15 vol %, such as from about 7 vol % to about 9 vol %. For many types of cathode input streams, the combined amount of CO₂ and O₂ can correspond to less than about 21 vol % of the input stream, such as less than about 15 vol % of the stream or less than about 10 vol % of the stream. An air stream containing oxygen can be combined with a CO₂ source that has low oxygen content. For example, the exhaust stream generated by burning coal may include a low oxygen content that can be mixed with air to form a cathode inlet stream.

In addition to CO₂ and O₂, a cathode input stream can also be composed of inert/non-reactive species such as N₂, H₂O, and other typical oxidant (air) components. For example, for a cathode input derived from an exhaust from a combustion reaction, if air is used as part of the oxidant source for the combustion reaction, the exhaust gas can include typical components of air such as N₂, H₂O, and other compounds in minor amounts that are present in air. Depending on the nature of the fuel source for the combustion reaction, additional species present after combustion based on the fuel source may include one or more of H₂O, oxides of nitrogen (NOx) and/or sulfur (SOx), and other compounds either present in the fuel and/or that are partial or complete combustion products of compounds present in the fuel, such as CO. These species may be present in amounts that do not poison the cathode catalyst surfaces though they may reduce the overall cathode activity. Such reductions in performance may be acceptable, or species that interact with the cathode catalyst may be reduced to acceptable levels by known pollutant removal technologies.

The amount of O₂ present in a cathode input stream (such as an input cathode stream based on a combustion exhaust) can advantageously be sufficient to provide the oxygen needed for the cathode reaction in the fuel cell. Thus, the volume percentage of O₂ can advantageously be at least 0.5 times the amount of CO₂ in the exhaust. Optionally, as necessary, additional air can be added to the cathode input to provide a sufficient oxidant for the cathode reaction. When some form of air is used as the oxidant, the amount of N₂ in the cathode exhaust can be at least about 78 vol %, e.g., at least about 88 vol %, and/or about 95 vol % or less. In some aspects, the cathode input stream can additionally or alternately contain compounds that are generally viewed as contaminants, such as H₂S or NH₃. In other aspects, the cathode input stream can be cleaned to reduce or minimize the content of such contaminants.

A suitable temperature for operation of an MCFC can be between about 450° C. and about 750° C., such as at least about 500° C., e.g., with an inlet temperature of about 550° C. and an outlet temperature of about 625° C. Prior to entering the cathode, heat can be added to or removed from the cathode input stream, if desired, e.g., to provide heat for other processes, such as reforming the fuel input for the anode. For example, if the source for the cathode input stream is a combustion exhaust stream, the combustion exhaust stream may have a temperature greater than a desired temperature for the cathode inlet. In such an aspect, heat can be removed from the combustion exhaust prior to use as the cathode input stream. Alternatively, the combustion exhaust could be at very low temperature, for example after a wet gas scrubber on a coal-fired boiler, in which case the combustion exhaust can be below about 100° C. Alternatively, the combustion exhaust could be from the exhaust of a gas turbine operated in combined cycle mode, in which the gas can be cooled by raising steam to run a steam turbine for additional power generation. In this case, the gas can be below about 50° C. Heat can be added to a combustion exhaust that is cooler than desired.

Additional Molten Carbonate Fuel Cell Operating Strategies

In some aspects, when operating an MCFC to cause alternative ion transport, the anode of the fuel cell can be operated at a traditional fuel utilization value of roughly 60% to 80%. When attempting to generate electrical power, operating the anode of the fuel cell at a relatively high fuel utilization can be beneficial for improving electrical efficiency (i.e., electrical energy generated per unit of chemical energy consumed by the fuel cell).

In some aspects, it may be beneficial to reduce the electrical efficiency of the fuel cell in order to provide other benefits, such as an increase in the amount of H₂ provided in the anode output flow. This can be beneficial, for example, if it is desirable to consume excess heat generated in the fuel cell (or fuel cell stack) by performing additional reforming and/or performing another endothermic reaction. For example, a molten carbonate fuel cell can be operated to provide increased production of syngas and/or hydrogen. The heat required for performing the endothermic reforming reaction can be provided by the exothermic electrochemical reaction in the anode for electricity generation. Rather than attempting to transport the heat generated by the exothermic fuel cell reaction(s) away from the fuel cell, this excess heat can be used in situ as a heat source for reforming and/or another endothermic reaction. This can result in more efficient use of the heat energy and/or a reduced need for additional external or internal heat exchange. This efficient production and use of heat energy, essentially in-situ, can reduce system complexity and components while maintaining advantageous operating conditions. In some aspects, the amount of reforming or other endothermic reaction can be selected to have an endothermic heat requirement comparable to, or even greater than, the amount of excess heat generated by the exothermic reaction(s) rather than significantly less than the heat requirement typically described in the prior art.

Additionally or alternately, the fuel cell can be operated so that the temperature differential between the anode inlet and the anode outlet can be negative rather than positive. Thus, instead of having a temperature increase between the anode inlet and the anode outlet, a sufficient amount of reforming and/or other endothermic reaction can be performed to cause the output stream from the anode outlet to be cooler than the anode inlet temperature. Further additionally or alternately, additional fuel can be supplied to a heater for the fuel cell and/or an internal reforming stage (or other internal endothermic reaction stage) so that the temperature differential between the anode input and the anode output can be smaller than the expected difference based on the relative demand of the endothermic reaction(s) and the combined exothermic heat generation of the cathode combustion reaction and the anode reaction for generating electrical power. In aspects where reforming is used as the endothermic reaction, operating a fuel cell to reform excess fuel can allow for production of increased synthesis gas and/or increased hydrogen relative to conventional fuel cell operation while minimizing the system complexity for heat exchange and reforming. The additional synthesis gas and/or additional hydrogen can then be used in a variety of applications, including chemical synthesis processes and/or collection/repurposing of hydrogen for use as a “clean” fuel.

The amount of heat generated per mole of hydrogen oxidized by the exothermic reaction at the anode can be substantially larger than the amount of heat consumed per mole of hydrogen generated by the reforming reaction. The net reaction for hydrogen in a molten carbonate fuel cell (H₂+½O₂=>H₂O) can have an enthalpy of reaction of about −285 kJ/mol of hydrogen molecules. At least a portion of this energy can be converted to electrical energy within the fuel cell. However, the difference (approximately) between the enthalpy of reaction and the electrical energy produced by the fuel cell can become heat within the fuel cell. This quantity of energy can alternatively be expressed as the current density (current per unit area) for the cell multiplied by the difference between the theoretical maximum voltage of the fuel cell and the actual voltage, or <current density>*(Vmax−Vact). This quantity of energy is defined as the “waste heat” for a fuel cell. As an example of reforming, the enthalpy of reforming for methane (CH₄+2H₂O=>4H₂+CO₂) can be about 250 kJ/mol of methane, or about 62 kJ/mol of hydrogen molecules. From a heat balance standpoint, each hydrogen molecule electrochemically oxidized can generate sufficient heat to generate more than one hydrogen molecule by reforming. In a conventional configuration, this excess heat can result in a substantial temperature difference from anode inlet to anode outlet. Instead of allowing this excess heat to be used for increasing the temperature in the fuel cell, the excess heat can be consumed by performing a matching amount of the reforming reaction. The excess heat generated in the anode can be supplemented with the excess heat generated by the combustion reaction in the fuel cell. More generally, the excess heat can be consumed by performing an endothermic reaction in the fuel cell anode and/or in an endothermic reaction stage heat integrated with the fuel cell.

Depending on the aspect, the amount of reforming and/or other endothermic reaction can be selected relative to the amount of hydrogen reacted in the anode in order to achieve a desired thermal ratio for the fuel cell. As used herein, the “thermal ratio” is defined as the heat produced by exothermic reactions in a fuel cell assembly (including exothermic reactions in both the anode and cathode) divided by the endothermic heat demand of reforming reactions occurring within the fuel cell assembly. Expressed mathematically, the thermal ratio (TH)=Q_(EX)/Q_(EN), where Q_(EX) is the sum of heat produced by exothermic reactions and Q_(EN) is the sum of heat consumed by the endothermic reactions occurring within the fuel cell. Note that the heat produced by the exothermic reactions can correspond to any heat due to reforming reactions, water gas shift reactions, combustion reactions (i.e., oxidation of fuel compounds) in the cathode, and/or the electrochemical reactions in the cell. The heat generated by the electrochemical reactions can be calculated based on the ideal electrochemical potential of the fuel cell reaction across the electrolyte minus the actual output voltage of the fuel cell. For example, the ideal electrochemical potential of the reaction in an MCFC is believed to be about 1.04 V based on the net reaction that occurs in the cell. During operation of the MCFC, the cell can typically have an output voltage less than 1.04 V due to various losses. For example, a common output/operating voltage can be about 0.7 V. The heat generated can be equal to the electrochemical potential of the cell (i.e. ˜1.04 V) minus the operating voltage. For example, the heat produced by the electrochemical reactions in the cell can be ˜0.34 V when the output voltage of ˜0.7 V is attained in the fuel cell. Thus, in this scenario, the electrochemical reactions would produce ˜0.7 V of electricity and ˜0.34 V of heat energy. In such an example, the ˜0.7 V of electrical energy is not included as part of Q_(EX). In other words, heat energy is not electrical energy.

In various aspects, a thermal ratio can be determined for any convenient fuel cell structure, such as a fuel cell stack, an individual fuel cell within a fuel cell stack, a fuel cell stack with an integrated reforming stage, a fuel cell stack with an integrated endothermic reaction stage, or a combination thereof. The thermal ratio may also be calculated for different units within a fuel cell stack, such as an assembly of fuel cells or fuel cell stacks. For example, the thermal ratio may be calculated for a fuel cell (or a plurality of fuel cells) within a fuel cell stack along with integrated reforming stages and/or integrated endothermic reaction stage elements in sufficiently close proximity to the fuel cell(s) to be integrated from a heat integration standpoint.

From a heat integration standpoint, a characteristic width in a fuel cell stack can be the height of an individual fuel cell stack element. It is noted that the separate reforming stage and/or a separate endothermic reaction stage could have a different height in the stack than a fuel cell. In such a scenario, the height of a fuel cell element can be used as the characteristic height. In this discussion, an integrated endothermic reaction stage can be defined as a stage heat integrated with one or more fuel cells, so that the integrated endothermic reaction stage can use the heat from the fuel cells as a heat source for reforming. Such an integrated endothermic reaction stage can be defined as being positioned less than 10 times the height of a stack element from fuel cells providing heat to the integrated stage. For example, an integrated endothermic reaction stage (such as a reforming stage) can be positioned less than 10 times the height of a stack element from any fuel cells that are heat integrated, or less than 8 times the height of a stack element, or less than 5 times the height of a stack element, or less than 3 times the height of a stack element. In this discussion, an integrated reforming stage and/or integrated endothermic reaction stage that represents an adjacent stack element to a fuel cell element is defined as being about one stack element height or less away from the adjacent fuel cell element.

A thermal ratio of about 1.3 or less, or about 1.15 or less, or about 1.0 or less, or about 0.95 or less, or about 0.90 or less, or about 0.85 or less, or about 0.80 or less, or about 0.75 or less, can be lower than the thermal ratio typically sought in use of MCFC fuel cells. In aspects of the invention, the thermal ratio can be reduced to increase and/or optimize syngas generation, hydrogen generation, generation of another product via an endothermic reaction, or a combination thereof.

In various aspects of the invention, the operation of the fuel cells can be characterized based on a thermal ratio. Where fuel cells are operated to have a desired thermal ratio, a molten carbonate fuel cell can be operated to have a thermal ratio of about 1.5 or less, for example about 1.3 or less, or about 1.15 or less, or about 1.0 or less, or about 0.95 or less, or about 0.90 or less, or about 0.85 or less, or about 0.80 or less, or about 0.75 or less. Additionally or alternately, the thermal ratio can be at least about 0.25, or at least about 0.35, or at least about 0.45, or at least about 0.50. Further additionally or alternately, in some aspects the fuel cell can be operated to have a temperature rise between the anode input and anode output of about 40° C. or less, such as about 20° C. or less, or about 10° C. or less. Still further additionally or alternately, the fuel cell can be operated to have an anode outlet temperature that is from about 10° C. lower to about 10° C. higher than the temperature of the anode inlet. Yet further additionally or alternately, the fuel cell can be operated to have an anode inlet temperature greater than the anode outlet temperature, such as at least about 5° C. greater, or at least about 10° C. greater, or at least about 20° C. greater, or at least about 25° C. greater. Still further additionally or alternately, the fuel cell can be operated to have an anode inlet temperature greater than the anode outlet temperature by about 100° C. or less, or about 80° C. or less, or about 60° C. or less, or about 50° C. or less, or about 40° C. or less, or about 30° C. or less, or about 20° C. or less.

Operating a fuel cell with a thermal ratio of less than 1 can cause a temperature drop across the fuel cell. In some aspects, the amount of reforming and/or other endothermic reaction may be limited so that a temperature drop from the anode inlet to the anode outlet can be about 100° C. or less, such as about 80° C. or less, or about 60° C. or less, or about 50° C. or less, or about 40° C. or less, or about 30° C. or less, or about 20° C. or less. Limiting the temperature drop from the anode inlet to the anode outlet can be beneficial, for example, for maintaining a sufficient temperature to allow complete or substantially complete conversion of fuels (by reforming) in the anode. In other aspects, additional heat can be supplied to the fuel cell (such as by heat exchange or combustion of additional fuel) so that the anode inlet temperature is greater than the anode outlet temperature by less than about 100° C. or less, such as about 80° C. or less, or about 60° C. or less, or about 50° C. or less, or about 40° C. or less, or about 30° C. or less, or about 20° C. or less, due to a balancing of the heat consumed by the endothermic reaction and the additional external heat supplied to the fuel cell.

The amount of reforming can additionally or alternately be dependent on the availability of a reformable fuel. For example, if the fuel only comprised H₂, no reformation would occur because H₂ is already reformed and is not further reformable. The amount of “syngas produced” by a fuel cell can be defined as a difference in the lower heating value (LHV) of syngas in the anode input versus an LHV of syngas in the anode output. Syngas produced LHV (sg net)=(LHV(sg out)−LHV(sg in)), where LHV(sg in) and LHV(sg out) refer to the LHV of the syngas in the anode inlet and syngas in the anode outlet streams or flows, respectively. A fuel cell provided with a fuel containing substantial amounts of H₂ can be limited in the amount of potential syngas production, since the fuel contains substantial amounts of already reformed H₂, as opposed to containing additional reformable fuel. The lower heating value is defined as the enthalpy of combustion of a fuel component to vapor phase, fully oxidized products (i.e., vapor phase CO₂ and H₂O product). For example, any CO₂ present in an anode input stream does not contribute to the fuel content of the anode input, since CO₂ is already fully oxidized. For this definition, the amount of oxidation occurring in the anode due to the anode fuel cell reaction is defined as oxidation of H₂ in the anode as part of the electrochemical reaction in the anode.

An example of a method for operating a fuel cell with a reduced thermal ratio can be a method where excess reforming of fuel is performed in order to balance the generation and consumption of heat in the fuel cell and/or consume more heat than is generated. Reforming a reformable fuel to form H₂ and/or CO can be an endothermic process, while the anode electrochemical oxidation reaction and the cathode combustion reaction(s) can be exothermic. During conventional fuel cell operation, the amount of reforming needed to supply the feed components for fuel cell operation can typically consume less heat than the amount of heat generated by the anode oxidation reaction. For example, conventional operation at a fuel utilization of about 70% or about 75% produces a thermal ratio substantially greater than 1, such as a thermal ratio of at least about 1.4 or greater, or 1.5 or greater. As a result, the output streams for the fuel cell can be hotter than the input streams. Instead of this type of conventional operation, the amount of fuel reformed in the reforming stages associated with the anode can be increased. For example, additional fuel can be reformed so that the heat generated by the exothermic fuel cell reactions can either be (roughly) balanced by the heat consumed in reforming and/or consume more heat than is generated. This can result in a substantial excess of hydrogen relative to the amount oxidized in the anode for electrical power generation and result in a thermal ratio of about 1.0 or less, such as about 0.95 or less, or about 0.90 or less, or about 0.85 or less, or about 0.80 or less, or about 0.75 or less.

Either hydrogen or syngas can be withdrawn from the anode exhaust as a chemical energy output. Hydrogen can be used as a clean fuel without generating greenhouse gases when it is burned or combusted. Instead, for hydrogen generated by reforming of hydrocarbons (or hydrocarbonaceous compounds), the CO₂ will have already been “captured” in the anode loop. Additionally, hydrogen can be a valuable input for a variety of refinery processes and/or other synthesis processes. Syngas can also be a valuable input for a variety of processes. In addition to having fuel value, syngas can be used as a feedstock for producing other higher value products, such as by using syngas as an input for Fischer-Tropsch synthesis and/or methanol synthesis processes.

In some aspects, the reformable hydrogen content of reformable fuel in the input stream delivered to the anode and/or to a reforming stage associated with the anode can be at least about 50% greater than the net amount of hydrogen reacted at the anode, such as at least about 75% greater or at least about 100% greater. Additionally or alternately, the reformable hydrogen content of fuel in the input stream delivered to the anode and/or to a reforming stage associated with the anode can be at least about 50% greater than the net amount of hydrogen reacted at the anode, such as at least about 75% greater or at least about 100% greater. In various aspects, a ratio of the reformable hydrogen content of the reformable fuel in the fuel stream relative to an amount of hydrogen reacted in the anode can be at least about 1.5:1, or at least about 2.0:1, or at least about 2.5:1, or at least about 3.0:1. Additionally or alternately, the ratio of reformable hydrogen content of the reformable fuel in the fuel stream relative to the amount of hydrogen reacted in the anode can be about 20:1 or less, such as about 15:1 or less or about 10:1 or less. In one aspect, it is contemplated that less than 100% of the reformable hydrogen content in the anode inlet stream can be converted to hydrogen. For example, at least about 80% of the reformable hydrogen content in an anode inlet stream can be converted to hydrogen in the anode and/or in an associated reforming stage(s), such as at least about 85%, or at least about 90%. Additionally or alternately, the amount of reformable fuel delivered to the anode can be characterized based on the lower heating value (LHV) of the reformable fuel relative to the LHV of the hydrogen oxidized in the anode. This can be referred to as a reformable fuel surplus ratio. In various aspects, the reformable fuel surplus ratio can be at least about 2.0, such as at least about 2.5, or at least about 3.0, or at least about 4.0. Additionally or alternately, the reformable fuel surplus ratio can be about 25.0 or less, such as about 20.0 or less, or about 15.0 or less, or about 10.0 or less.

Example

Molten carbonate fuel cells (size of 3 cm²) were fabricated using similar methodologies, but with two different types of cathodes. The fuel cells had a structure similar to the structure described in FIG. 3 . A first type of fuel cell was formed with a dual-layer cathode. The first layer of the dual-layer cathode, adjacent to the electrolyte, was formed using nickel particles. The second layer was formed using a mixture of nickel and 15 vol % lithium carbonate particles. Because of the dual-layer structure, the first layer had an average pore diameter of less than 4.0 μm, while the second layer (adjacent to the cathode collector) had an average pore diameter of 6.0 μm or more. The second type of fuel cell was formed using nickel particles, so the average pore size throughout the cathode was less than 4.0 μm. Fuel cells constructed with Li/K and Li/Na as electrolyte were constructed.

The fuel cells were operated using an anode gas corresponding to 72.8% H₂, 18.2% CO₂, and 9% H₂O. The cathode gas was 18.5% CO₂, 12.1% O₂, 66.4% N₂, and 3% H₂O. The fuel cells were operated to generate 160 mA/cm² at a relatively low fuel utilization (˜5%) and low CO₂ utilization (˜5%).

Cell voltage and cathode polarizations were measured at different temperatures to evaluate the performance of the dual-layer cathode vs. the single layer (baseline) design. FIG. 5 shows that the dual-layer cathode design unexpectedly exhibited 30 mV to 40 mV lower polarization under molten carbonate fuel cell operating conditions than the single layer cathode fuel cells. The effect is larger at temperatures of less than 600° C. This can be beneficial for enabling lower temperature fuel cell stack operation and/or for extending cell life due to reduced degradation rate. Without being bound by any particular theory, it is believed that the unexpected improvement displayed by the double layer cathode stems mainly from lower mass-transfer resistance due to the presence of stable large pores in the cathode layer facing the current collector.

ADDITIONAL EMBODIMENTS Embodiment 1

A method for producing electricity, the method comprising: contacting an anode of a molten carbonate fuel cell with an anode input stream; contacting a second cathode layer of a cathode of the molten carbonate fuel cell with a cathode inlet stream comprising O₂ and CO₂, the second cathode layer comprising an average pore diameter of 5.5 μm or more, the cathode further comprising a first cathode layer adjacent to an electrolyte of the fuel cell, the first cathode layer having an average pore diameter of 4.5 μm or less; and operating the molten carbonate fuel cell at a current density of 60 mA/cm² or more (or 100 mA/cm² or more, or 150 mA/cm² or more) to generate electricity, an anode exhaust comprising H₂, CO, and CO₂, and a cathode exhaust comprising CO₂.

Embodiment 2

The method of Embodiment 1, wherein the molten carbonate fuel cell is operated at an average temperature of 650° C. or less, or 620° C. or less, or 600° C.

Embodiment 3

The method of any of the above embodiments, wherein the second layer of the cathode of the molten carbonate fuel cell is formed by sintering a layer comprising 1.0 vol % to 30 vol % of a lithium pore-forming compound, or wherein the second layer of the cathode of the molten carbonate fuel cell is formed by sintering a layer comprising 1.0 vol % to 30 vol % of particles comprising a lithium pore-forming compound, or a combination thereof, the lithium pore-forming compound optionally comprising particles having an average particle size of 4.0 μm to 10 μm.

Embodiment 4

The method of any of the above embodiments, wherein the first cathode layer is formed by sintering a layer comprising particles having an average particle size of 1.0 μm to 3.0 μm.

Embodiment 5

The method of any of the above embodiments, wherein the second cathode layer comprises an average pore diameter of 6.0 μm to 10 μm, or 7.0 μm to 9.0 μm.

Embodiment 6

The method of any of the above embodiments, wherein the cathode exhaust comprises 2.0 vol % CO₂ or less, 1.0 vol % O₂ or more, and 1.0 vol % H₂O or more; or a combination thereof.

Embodiment 7

The method of any of the above embodiments, wherein the cathode inlet comprises 5.0 vol % CO₂ or less; or wherein the cathode exhaust comprises 1.0 vol % CO₂ or less, or a combination thereof.

Embodiment 8

The method of any of the above embodiments, wherein the molten carbonate fuel cell is operated at a transference of 0.95 or less, or 0.90 or less.

Embodiment 9

A method for forming a molten carbonate fuel cell, comprising: depositing a first layer of first cathode precursor particles having an average particle size of 1.0 μm to 3.0 μm; depositing a second layer comprising 1.0 vol % to 30 vol % of lithium pore-forming compound particles and 70 vol % or less of second cathode precursor particles, the lithium pore-forming compound particles having an average particle size of 4.0 μm to 10 μm, the second cathode precursor particles having an average particle size of 1.0 μm to 3.0 μm; and sintering the first layer and the second layer to form a cathode comprising a first cathode layer comprising an average pore size of 4.5 μm or less and a second cathode layer comprising an average pore size of 5.5 μm or more, or 5.5 μm to 10 μm, or 6.0 μm to 10 μm, the first cathode precursor particles and the second cathode precursor particles optionally having substantially the same composition.

Embodiment 10

The method of Embodiment 9, wherein a porosity of the first layer of cathode precursor particles is 70% to 80% and a porosity of the second layer of cathode precursor particles is 78% to 88%; or wherein a porosity of the first cathode layer is 50% to 62% and a porosity of the second cathode layer is 65% to 77%; or a combination thereof.

Embodiment 11

A molten carbonate fuel cell, comprising: an anode adjacent to an anode collector; an electrolyte matrix comprising an electrolyte; and a cathode comprising a first cathode layer adjacent to the electrolyte matrix and a second cathode layer adjacent to a cathode collector, the first cathode layer comprising an average pore diameter of 4.5 μm or less, the second cathode layer comprising an average pore diameter of 5.5 μm or more, or 5.5 μm to 10 μm, or 6.0 μm to 10 μm.

Embodiment 12

The method of any of Embodiments 1-10 or the molten carbonate fuel cell of Embodiment 11, wherein the first cathode layer comprises lithiated nickel oxide, or wherein the second cathode layer comprises lithiated nickel oxide, or a combination thereof.

Embodiment 13

The method of any of Embodiments 1-10 or 12, or the molten carbonate fuel cell of Embodiment 11 or 12, wherein 70 wt % or more of the second cathode layer comprises the composition of the first layer of the cathode (or 90 wt % or more).

Embodiment 14

The method of any of Embodiments 1-10 or 12-13, or the molten carbonate fuel cell of any of Embodiments 11-13, wherein the first cathode layer comprises a thickness of 250 μm to 400 μm, or wherein the second cathode layer comprises a thickness of 500 μm to 800 μm, or a combination thereof.

Embodiment 15

A molten carbonate fuel cell formed according to the method of any of Embodiments 9, 10, or 12-14.

All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

Although the present invention has been described in terms of specific embodiments, it is not necessarily so limited. Suitable alterations/modifications for operation under specific conditions should be apparent to those skilled in the art. It is therefore intended that the following claims be interpreted as covering all such alterations/modifications that fall within the true spirit/scope of the invention. 

The invention claimed is:
 1. A method for producing electricity, the method comprising: contacting an anode of a molten carbonate fuel cell with an anode input stream; contacting a second cathode layer of a cathode of the molten carbonate fuel cell with a cathode inlet stream comprising O₂ and CO₂, the second cathode layer comprising an average pore diameter in a range of 5.5 μm to 10 μm, the cathode further comprising a first cathode layer adjacent to an electrolyte of the fuel cell, the first cathode layer having an average pore diameter in a range of 1 μm to 4.5 μm; and operating the molten carbonate fuel cell at a current density of 60 mA/cm² or more to generate electricity, an anode exhaust comprising H₂, CO, and CO₂, and a cathode exhaust comprising CO₂, wherein the second cathode layer of the molten carbonate fuel cell is formed by sintering a layer comprising 1.0 vol % to 30 vol % of a lithium pore-forming compound, or wherein the second cathode layer of the molten carbonate fuel cell is formed by sintering a layer comprising 1.0 vol % to 30 vol % of particles comprising a lithium pore-forming compound, or a combination thereof.
 2. The method of claim 1, wherein the first cathode layer comprises lithiated nickel oxide, or wherein the second cathode layer comprises lithiated nickel oxide, or a combination thereof.
 3. The method of claim 1, wherein 70 wt % or more of the second cathode layer comprises a composition of the first cathode layer.
 4. The method of claim 1, wherein the first cathode layer comprises a thickness of 250 μm to 400 μm, or wherein the second cathode layer comprises a thickness of 500 μm to 800 μm, or a combination thereof.
 5. The method of claim 1, wherein the molten carbonate fuel cell is operated at an average temperature of 650° C. or less.
 6. The method of claim 1, wherein the lithium pore-forming compound comprises particles having an average particle size of 4.0 μm to 10 μm.
 7. The method of claim 1, wherein the first cathode layer is formed by sintering a layer comprising particles having an average particle size of 1.0 μm to 3.0 μm.
 8. The method of claim 1, wherein the second cathode layer comprises an average pore diameter of 6.0 μm to 10 μm.
 9. The method of claim 1, wherein the cathode exhaust comprises 2.0 vol % CO₂ or less, 1.0 vol % O₂ or more, and 1.0 vol % H₂O or more; or a combination thereof.
 10. The method of claim 1, wherein the cathode inlet stream comprises 5.0 vol % CO₂ or less, or wherein the cathode exhaust comprises 1.0 vol % CO₂ or less, or a combination thereof. 